Organosilicon cinnamates

ABSTRACT

SILANES AND SILOXANES CONTAINING THE GROUP   $SIR&#39;&#39;S(CH2)3OOCCH=CHC6H5   ARE PREPARED BY THE ADDITION OF ALLYL CINNAMATE TO THE CORRESPONDING MERCAPTO SILANE OR SILOXANE. THE COMPOSITIONS ARE USEFUL AS SUNSCREEN AGENTS IN PROTECTION COATINGS AND IN COSMETIC APPLICATIONS.

United States Patent "ice US. Cl. 260-448.2 N 2 Claims ABSTRACT OF THEDISCLOSURE Silanes and siloxanes containing the group are prepared bythe addition of allyl cinnamate to the corresponding mercapto silane orsiloxane. The compositions are useful as sunscreen agents in protectivecoatings and in cosmetic applications.

Attempts to prepare siloxanes having an ester substituent attached tosilicon by the addition of an allyl ester of a carboxylic acid to an SiHcontaining siloxane, generally result in the formation of large amountsof propylene and the formation of SiOOCR groups. It has been found,however, that quantitative yields of the desired ester are obtained whenone employs a mercapto siloxane in place of the SiH containing siloxane.

It is the object of this invention to provide cinnamate modified silanesand siloxanes in good yields which materials are excellent sunscreenagents for cosmetic and other applications.

This invention relates to compounds of the formula (1) X RnSiR'S(CH2)3OOCCH=CHCBH5 in which X is a hydrolyzable group free ofcarbon-carbon aliphatic unsaturation or an OH group,

R is a monovalent hydrocarbon or a monovalent halohydrocarbon radicalfree of aliphatic unsaturation,

R' is a divalent hydrocarbon radical of 1 to 18 carbon atoms, free ofaliphatic unsaturation or a silacyclopentane radical,

R" is a monovalent hydrocarbon or halohydrocarbon radical, ahydrolyzable group, an H atom or OH,

n is an integer from 0 to 2,

m is an integer from 0 to 2, the sum of m+n being not greater than 2,and

a is an integer from 0 to 3.

The compositions of this invention are prepared by reacting allylcinnamate with a silane or siloxane containing the SiR'SH group in thepresence of a free radical generator such as peroxides, such as benzoylperoxide, azonitriles such as aZo-bis-isobutyronitrile, ultravioletlight or heat.

The compositions can be silanes, homopolymeric siloxanes in which eachsilicon has a cinnamate group attached thereto, copolymeric siloxanes inwhich each silicon atom has a cinnamate group attached thereto andcopolymers 1 The term hydrolyzable group means one which reacts withwater at room temperature to produce 551011 and XH.

3,767,690 Patented Oct. 23, 1973 in which at least one silicon atom hasa cinnamate group attached thereto and the remaining silicon atoms donot. When Z represents the -R'S(CH OOCCH=CHC H group, the siloxane unitsWithin the scope of this invention are ZSiO ZR SiO ZRSiO, ZXSiO, ZX SiOand ZRXSiO and copolymers of any combination of the above with eachother and copolymers of any combination of the above with siloxane unitsto the formula R" SiO R SiO, R"SiO and SiO units. Thus the siloxanes ofthis invention can be in the form of fluids, rubbers or resins.

For the purpose of this invention X can be any hydrolyzable group suchas organic groups free of aliphatic unsaturation such as alkoxy radicalssuch as methoxy, ethoxy, isopropoxy, octadecyloxy, cyclohexyloxy,cyclopentyloxy, beta-methoxy ethoxy, beta-ethoxy ethoxy, or CH O(CH CHO),, where n is 2 or 3; aryloxy radicals such as phenoxy, tolyloxy, ornaphthyloxy; acyloxy radicals such as formyloxy, acetoxy, propionyloxy,or hexoyloxy; ketoxime radicals of the formula -ON=CA in which A is ahydrocarbon or halohydrocarbon radical such as methyl, ethyl, octadecyl,cyclohexyl, cyclopentyl, chloroethyl, chlorophenyl, etc.; amino radicalsof the formula NA where A is above defined; amineoxy radicals of theformula ONA where A is above defined; and amido radicals of the formula-NI-IOCA where A is as above defined and inorganic hydrolyzable groupssuch as halogen atoms such as chlorine, bromine, iodine or fluorine orthe sulphate radical.

For the purpose of this invention R can be any monovalent hydrocarbon orhalohydrocarbon radical free of aliphatic unsaturation such as alkylradicals such as methyl, ethyl, isopropyl, or octadecyl; cycloaliphaticradicals such as cyclohexyl, cyclopentyl, or methylcyclohexyl; arylhydrocarbon radicals such as phenyl, naphthyl, xenyl, tolyl, or xylyland aralkyl radicals such as benzyl, betaphenyl ethyl or beta-phenylpropyl. R can also be any halogenated monovalent hydrocarbon radicalsuch as trifiuoropropyl, chloropropyl, iodomethyl, chlorophenyl,dibromophenyl, fiuorophenyl, chloronaphthyl, or hexachloroxenyl.

For the purpose of this invention R can be any divalent hydrocarbonradical such as methylene, dimethylene, trimethylene, octadecamethylene,isobutylene,

phenylene, naphthylene, tolylene, cyclohexylene, or cyclopentylene.

For the purpose of this invention R" can be any monovalent hydrocarbonor halohydrocarbon radical such as those shown for R above and inaddition R" can be any alkenyl radical such as vinyl, allyl, hexenyl, orany cycloalkenyl radical such as cyclohexenyl or cyclopentenyl. Inaddition R" can be any of the hydrolyzable groups shown for X above andit can be the hydrogen atom or a hydroxyl radical.

The mercapto silanes and siloxanes used as starting materials for thisinvention are well known materials as exemplified by such U.S. Pats. as3,465,015 and 3,590,- 065, French Pats. such as 2,056,526 and 2,056,527and the copending application of Gary E. LeGrow, Ser. No. 54,532, filedJuly 13, 1970, entitled, Silacyclopentane Thiols and Thiolates, now Pat.No. 3,655,713. All of these patents and the copending application arehereby incorporated in this disclosure by reference.

The compositions of this invention can be used in the preparation ofcosmetic materials and thereby increase the resistance of the skin tosolar radiation. They can also be incorporated in protective coatingssuch as paints in order to increase the life of those coatings and topro long the life of the substrate protected thereby.

The following examples are illustrative only and should not be construedas limiting the invention which is properly delineated in the appendedclaims.

EXAMPLE 1 To 2500 m1. of rapidly stirred water was added a mixture of217 g. of trimethyl monochloro silane, 480 g. of dimethyl dimethoxysilane and 180 g. of S-mercaptopropyl methyl dimethoxy silane over aperiod of 1 hour. An exotherm to 45 C. occurred. The reaction mixturewas cooled, separated and the organic layer was washed with water untilacid-free and dried over anhydrous sodium sulphate. The water-Whiteproduct had the properties viscosity 3.12 es. and N of 14135. Tests withnuclear magnetic resonance showed it to be the expected mercapto propylsiloxane copolymer.

147 g. of the fluid prepared above was mixed with 47 g. of allylcinnamate and 0.25 g. of azo-bis-isobutyronitrile. The mixture washeated and stirred for 24 hours at 80 C. Color developed in the productbut was removed with an activated charcoal treatment followed byfiltration. The low boiling species were removed by heating at 50 C. at1 mm. pressure giving 150 gm. of a fluid having a viscosity of 50 cs.This was shown by nuclear magnetic resonance to be of the formula Me SiOM6 310 MeSi{--(CH S (CH OOCCH Ultraviolet absorption was run on thefluid and the results are as follows:

Lambda max. m Epsilon 333 456 EXAMPLE 2 The following cinnamates areobtained when the following mercaptans are reacted with allylcinnarnatein accordance with the procedure of Example 1. Y represents the (CHOOCCH:CHC H radical. The following abbreviations are used below: Me formethyl, Et for ethyl, Bu for butyl, Ph for phenyl and Vi for vinyl.

CMBHQHZ) Sl(CH2)3SH H S (CHiOaSiO 4S1 Liter 11 11 Al ie: HS(CH2)3S1' 0%1OSKCHMSH Me in CHgCHzCF:

HS(CH1)3S1 0 Si OH Me in 2 mHn HSCHgSl. O Bil OMe Cupolymer of 10 molpercent HS(CH2):1SiO1.e 20 mol percent hIeSiOrs 30 11101 percentPhSiO1.5

20 mol percent Ph2SiO 20 mol percent MezSiO copolymer of 10 mol percentHS(CH2):;SiO1.n

5 mol percent ViSiOLs 20 mol percent CeHnSlOrfi 10 mol percentPhCllH-lSiOLB 20 mol percent PhMeSiO 35 mol percent MezSiO CHBSH M62) HOSiO Sio ioau Cinnamates (MeOivsSiCHzSY (EtOhPhSHCHflraSY(MeCOOlEtzSiCHzCHaSY lllle (PhCH-!)(1\KB)(HO) SiCHzCHCHzSY2C=NO)3SiCaH4SY CHzCHzCFa (MeO CHzCHzOhSiCaHnS Y CHzCHzCHgCl (EtzNO):SlC HzCHzCHzSY (MQCONH)2(C13H37)SiCHzCHzCuHqSY Mo: [YE CH2)3S iO] Sl Me:Ph Me: YS(CHz)3 l Oi OKCHzhSY the m CHgCHgCFa YS (CI-IgkSi 0S1 OH Me 10I C mHzi YSCHzSl O Si 0M8 copolymer of 10 mol percent YS (CH2)8S101.5

20 mol percent L\II2SiO1.5

30 mol percent PhSiOLE 20 mol percent PhzSiO 20 mol percent MezSiOcopolymer of 10 mol percent YSUSEMSiOLs 5 mol percent Vi $1015 20 molpercent CflHtlSiOLES 10 mol percent PhCflH4SiO1-5 20 mol percent PhMeSiO35 mol percent Me-2Si0 CH SY ill/lei) H0 810 SiO H EXAMPLE 3 When amixture of 5 mol percent 5 That which is claimed is: 1. A composition ofmatter selected from the group consisting of 1 X R SiR'S (CH OOCCH=CHC Hand (3) copolymers containing at least one unit, the remaining siloxaneunits in said copolymer being of the unit formula R"aSiO 6 atoms, freeof aliphatic unsaturation or a silacyclopentane radical, R" is amonovalent hydrocarbon or halohydrocarbon radical, a hydrolyzable group,a hydrogen atom or OH, X, R and R" containing from 1 to 18 carbon atoms,n is an integer from 0 to 2, m is an integer from 0 to 2, the sum of m+nbeing not greater than 2, and a is an integer from 0 to 3.

2. A copolymer of claim 1 in which m is O, R is methyl, n is 1, R is-(CH R is methyl and a is 2 0r 3.

References Cited UNITED STATES PATENTS 1/1967 Lamoreaux 260-46.5 G5/1972 LeGrow 260-448.2 N

PATRICK P. GARVIN, Primary Examiner P. F. SHAVER, Assistant Examiner US.Cl. X.R.

